KR102695611B1 - Manufacturing method of starch using rice washing water - Google Patents

Manufacturing method of starch using rice washing water Download PDF

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KR102695611B1
KR102695611B1 KR1020210181481A KR20210181481A KR102695611B1 KR 102695611 B1 KR102695611 B1 KR 102695611B1 KR 1020210181481 A KR1020210181481 A KR 1020210181481A KR 20210181481 A KR20210181481 A KR 20210181481A KR 102695611 B1 KR102695611 B1 KR 102695611B1
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starch
mixing
washing water
water
distilled water
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KR20230092247A (en
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송지영
박희전
정소희
문세훈
백만희
서병철
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재단법인 고창식품산업연구원
(주)엄지식품
순천향대학교 산학협력단
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L7/00Cereal-derived products; Malt products; Preparation or treatment thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2250/00Food ingredients
    • A23V2250/02Acid

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

본 발명은 쌀세정수를 이용한 전분의 제조방법에 관한 것으로, 더욱 상세하게는 쌀세정수에서 전분을 회수하는 전분회수단계, 상기 전분회수단계를 통해 회수된 전분에 증류수를 혼합하는 증류수혼합단계, 상기 증류수혼합단계를 통해 제조된 혼합물에 무수옥테닐 호박산과 수산화나트륨을 혼합하는 호박산혼합단계, 상기 호박산혼합단계를 통해 제조된 혼합물을 중화하는 중화단계, 상기 중화단계를 통해 중화된 혼합물을 원심분리하는 원심분리단계 및 상기 원심분리단계를 통해 분리된 전분을 세척한 후에 열풍건조하는 세척건조단계로 이루어진다.
상기의 과정을 통해 이루어지는 전분의 제조방법은 유화 안정성 및 냉해동 안정성이 월등하게 향상된 전분을 제공한다.
The present invention relates to a method for manufacturing starch using rice washing water, and more specifically, the method comprises a starch recovery step of recovering starch from rice washing water, a distilled water mixing step of mixing distilled water with the starch recovered through the starch recovery step, a succinic acid mixing step of mixing anhydrous octenyl succinic acid and sodium hydroxide with the mixture prepared through the distilled water mixing step, a neutralization step of neutralizing the mixture prepared through the succinic acid mixing step, a centrifugation step of centrifuging the mixture neutralized through the neutralization step, and a washing and drying step of washing the starch separated through the centrifugation step and then drying it with hot air.
The method for manufacturing starch through the above process provides starch with significantly improved emulsification stability and freeze-thaw stability.

Description

쌀세정수를 이용한 전분의 제조방법 {MANUFACTURING METHOD OF STARCH USING RICE WASHING WATER}MANUFACTURING METHOD OF STARCH USING RICE WASHING WATER

본 발명은 쌀세정수를 이용한 전분의 제조방법에 관한 것으로, 더욱 상세하게는 유화 안정성 및 냉해동 안정성이 월등하게 향상된 전분을 제공하는 쌀세정수를 이용한 전분의 제조방법에 관한 것이다.The present invention relates to a method for producing starch using rice washing water, and more specifically, to a method for producing starch using rice washing water which provides starch having significantly improved emulsification stability and freeze-thaw stability.

최근 1인 가구 증가와 같은 사회적 변화와 식습관 변화 등으로 인해 국민 1일당 연간 쌀 소비량은 감소하는 추세이지만 쌀을 원료로 하는 HMR 제품 증가와 식사대용 및 간식 용도의 쌀 가공식품 수요가 증가하고 있다(Korea Agro-Fisheries & Food Trade Corporation. 2021).Due to social changes such as the recent increase in single-person households and changes in eating habits, the annual rice consumption per person per day is on the decline, but the demand for HMR products using rice as a raw material and processed rice foods for meal replacement and snack purposes is increasing (Korea Agro-Fisheries & Food Trade Corporation. 2021).

쌀 가공식품은 제조공정중 쌀을 세척하는 과정이 필요하며 이때 발생하는 쌀세정수는 화학적, 생물학적 산소요구량이 높아 수질오염의 원인이 되어 이를 처리하는데 비용이 발생한다. 환경부(2021)에서는 2019년도 기준 업종별 폐수배출업소 현황조사결과 운수세차, 금속가공, 석유화학, 음식료 순으로 음식료 업종이 4번째로 높았고, BOD 발생 부하량은 1일 551,000 kg으로 음식료 업종이 가장 높았으며 BOD 배출 부하량은 1일 2,700 kg으로 두번째로 높았다고 발표하였다. Rice-processed foods require a rice-washing process during the manufacturing process, and the rice-washing water generated during this process has high chemical and biological oxygen demand, which causes water pollution and incurs costs for its treatment. The Ministry of Environment (2021) announced that according to the results of a survey on wastewater discharge businesses by industry in 2019, the food and beverage industry ranked fourth in that order, followed by transportation and car washing, metal processing, petrochemicals, and food and beverage. The food and beverage industry had the highest BOD generation load of 551,000 kg per day, and the BOD emission load was the second highest at 2,700 kg per day.

또한, 쌀 가공공정중 발생되는 쌀세정수 중에는 총 고형분 0.32%, 가용성 고형분 0.11%가 함유되어 있으며 쌀 사용량대한 손실량으로 계산하면 총 사용한 쌀의 1.65%, 수용성 고형분 0.6%에 해당된다(Shin DH 1997). 쌀세정수는 비타민 B군, 지질, 전분질 등 인체에 유익한 영양성분을 함유하고 있으며, Kim MJ 등(2011)은 쌀을 씻는 과정중 쌀의 영양성분 일부가 세정수로 이동하여 쌀세정수에 탄수화물, 지방, 단백질 등의 고형성분이 0.7% 정도 함유하였고, 건조시킨 경우 탄수화물 40.9%, 단백질 22.9%, 지질 19.6%라고 하였으며 전자현미경 관찰 결과 전분입자 형태는 손상되지 않았다고 보고하였다. In addition, the rice washing water generated during the rice processing process contains 0.32% of total solids and 0.11% of soluble solids, which corresponds to 1.65% of the total rice used and 0.6% of soluble solids when calculated as the loss per unit of rice usage (Shin DH 1997). The rice washing water contains nutrients beneficial to the human body, such as vitamin B group, lipids, and starch, and Kim MJ et al. (2011) reported that during the rice washing process, some of the nutrients of the rice move to the washing water, and the rice washing water contains about 0.7% of solid components such as carbohydrates, fat, and protein, and when dried, it contained 40.9% of carbohydrates, 22.9% of protein, and 19.6% of lipids, and the results of electron microscope observation showed that the starch particle shape was not damaged.

유익한 성분을 다량 함유하고 있는 쌀세정수는 재활용될 수 있는 자원이지만 생활하수의 오염원으로 알려져 있어 많은 비용을 지불하고 버려지고 있다. 폐기되는 일부만이 사료, 화장품, 의약품 등의 원료로 이용되고 있어 재활용 분야를 확대하기 위해 발효공정을 적용하고 기능성 소재로 개발하려는 시도가 있었고(Cho JI 등 2004, Kim MJ 등 2011, Lee D 2014), 단백질 등의 유효성분을 회수하려는 연구가 있었으나(Chung KY & Park SH 2002,) 세정수에 다량 함유된 전분에 대한 연구는 지금까지 거의 이루어지지 않고 있다.Rice washing water, which contains a large amount of beneficial ingredients, is a recyclable resource, but it is known as a source of pollution in domestic wastewater, so it is being discarded at a high cost. Only a portion of the discarded water is used as raw materials for feed, cosmetics, and medicines, so there have been attempts to apply a fermentation process to expand the recycling area and develop it into a functional material (Cho JI et al. 2004, Kim MJ et al. 2011, Lee D 2014), and there have been studies to recover effective ingredients such as proteins (Chung KY & Park SH 2002,). However, little research has been conducted on starch, which is contained in large amounts in washing water, to date.

한편, 전분은 식물이 광합성을 통해 만든 포도당을 식물체의 각 부위에 입자형태로 저장하는 성분으로 자연식품이나 가공과정 중에 재료로서 또는 품질을 유지하기 위해 첨가물로 사용되기도 한다. 특히 변성전분은 전분을 물리화학적 및 효소적 방법으로 변성시켜 용도에 따라 새로운 성질을 갖도록 제조하여 이용하고 있다(Shin MS 등 2021). 그중 옥테닐호박산전분(OSA전분)은 알칼리 조건 하에 전분과 옥테닐호박산(OSA)을 에스테르화시킨 화학적 변성전분으로, 생전분의 친수성 구조에 소수성인 OSA group이 결합되어 양극성을 가진 전분으로 전환되므로써 유화액에서 물과 기름사이의 계면장력을 낮추어 유화안정화에 기여한다(Nilsson L & Bergenstahl B 2006, Nilsson L & Bergenstahl B 2007). Meanwhile, starch is a component that stores glucose produced by plants through photosynthesis in the form of particles in each part of the plant, and is also used as a natural food or as a material during the processing process or as an additive to maintain quality. In particular, modified starch is manufactured and used by modifying starch through physicochemical and enzymatic methods to have new properties depending on the use (Shin MS et al. 2021). Among them, octenyl succinate starch (OSA starch) is a chemically modified starch that esterifies starch and octenyl succinic acid (OSA) under alkaline conditions. The hydrophobic OSA group is combined with the hydrophilic structure of raw starch to convert it into starch with bipolarity, thereby lowering the interfacial tension between water and oil in the emulsion and contributing to emulsion stabilization (Nilsson L & Bergenstahl B 2006, Nilsson L & Bergenstahl B 2007).

본 발명에서는 쌀세정수를 식품첨가물 소재로 활용하기 위해 세정수에서 분말과 전분을 분리하여 쌀 낟알에서 분리된 전분과의 특성을 비교하고 옥테닐호박산전분을 제조하여 변성전분 및 유화제, 안정제와 같은 식품첨가물 소재로써의 활용가능성을 검토하고자 하였다. 또한 옥테닐호박산전분의 특성을 다양화하기 위해 어닐링처리를 병행하여 유화안정성, 냉해동 안정성을 확인하였으며 유화제로써의 활용도와 찐만두용 만두피반죽에 첨가하여 냉해동안정성 개선에 대한 활용가능성을 검토하였다.In the present invention, in order to utilize rice washing water as a food additive material, powder and starch were separated from washing water, and the characteristics were compared with the starch separated from rice grains, and octenyl succinate starch was manufactured to examine the possibility of utilization as a food additive material such as a modified starch and an emulsifier and stabilizer. In addition, in order to diversify the characteristics of octenyl succinate starch, annealing treatment was performed in parallel to confirm the emulsification stability and freeze-thaw stability, and the possibility of utilization as an emulsifier and improvement of freeze-thaw stability by adding it to dumpling skin dough for steamed dumplings was examined.

한국특허등록 제10-1461639호(2014.11.07.)Korean Patent Registration No. 10-1461639 (2014.11.07.) 한국특허등록 제10-1848840호(2018.04.09.)Korean Patent Registration No. 10-1848840 (April 9, 2018)

본 발명의 목적은 유화 안정성 및 냉해동 안정성이 월등하게 향상된 전분을 제조할 수 있는 쌀세정수를 이용한 전분의 제조방법을 제공하는 것이다.The purpose of the present invention is to provide a method for producing starch using rice washing water, which can produce starch having significantly improved emulsion stability and freeze-thaw stability.

본 발명의 목적은 쌀세정수에서 전분을 회수하는 전분회수단계, 상기 전분회수단계를 통해 회수된 전분에 증류수를 혼합하는 증류수혼합단계, 상기 증류수혼합단계를 통해 제조된 혼합물에 무수옥테닐 호박산과 수산화나트륨을 혼합하는 호박산혼합단계, 상기 호박산혼합단계를 통해 제조된 혼합물을 중화하는 중화단계, 상기 중화단계를 통해 중화된 혼합물을 원심분리하는 원심분리단계 및 상기 원심분리단계를 통해 분리된 전분을 세척한 후에 열풍건조하는 세척건조단계로 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법을 제공함에 의해 달성된다.The object of the present invention is achieved by providing a method for manufacturing starch using rice washing water, characterized in that the method comprises a starch recovery step of recovering starch from rice washing water, a distilled water mixing step of mixing distilled water with the starch recovered through the starch recovery step, a succinic acid mixing step of mixing anhydrous octenyl succinic acid and sodium hydroxide with the mixture prepared through the distilled water mixing step, a neutralization step of neutralizing the mixture prepared through the succinic acid mixing step, a centrifugation step of centrifuging the mixture neutralized through the neutralization step, and a washing and drying step of washing the starch separated through the centrifugation step and then drying it with hot air.

본 발명의 바람직한 특징에 따르면, 상기 증류수혼합단계와 상기 호박산혼합단계 사이에는 상기 증류수혼합단계를 통해 제조된 혼합물을 어닐링하는 어닐링단계가 더 진행되며, 상기 어닐링단계는 40 내지 50℃의 온도에서 20 내지 30시간 동안 이루어지는 것으로 한다.According to a preferred feature of the present invention, an annealing step of annealing the mixture prepared through the distilled water mixing step is further performed between the distilled water mixing step and the succinic acid mixing step, and the annealing step is performed at a temperature of 40 to 50°C for 20 to 30 hours.

본 발명의 더 바람직한 특징에 따르며, 상기 전분회수단계는 쌀세정수를 원심분리한 후에 침전물을 회수하고, 회수된 침전물을 질량농도가 0.2%인 수산화나트륨수용액으로 정제한 후에 1N 염산용액으로 중화하고 세척 및 건조하여 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the starch recovery step is performed by centrifuging rice washing water, recovering a precipitate, purifying the recovered precipitate with a sodium hydroxide aqueous solution having a mass concentration of 0.2%, neutralizing it with a 1 N hydrochloric acid solution, washing it, and drying it.

본 발명의 더욱 바람직한 특징에 따르면, 상기 증류수혼합단계는 상기 전분회수단계를 통해 제조된 전분 100 중량부에 증류수 180 내지 300 중량부를 혼합하여 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the distilled water mixing step is performed by mixing 180 to 300 parts by weight of distilled water with 100 parts by weight of starch manufactured through the starch recovery step.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 호박산혼합단계는 상기 증류수혼합단계를 통해 제조된 혼합물에 함유된 전분 100 중량부 대비 무수옥테닐 호박산 2 내지 4 중량부를 혼합하고, 수산화나트륨을 혼합하여 혼합물의 pH를 8 내지 9로 유지한 상태에서 5 내지 7시간 동안 반응하여 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the succinic acid mixing step is performed by mixing 2 to 4 parts by weight of anhydrous octenyl succinic acid relative to 100 parts by weight of starch contained in the mixture prepared through the distilled water mixing step, mixing sodium hydroxide, and reacting the mixture for 5 to 7 hours while maintaining the pH of the mixture at 8 to 9.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 중화단계는 상기 호박산혼합단계를 통해 제조된 혼합물에 1N의 염산을 혼합하여 혼합물의 pH를 6.9 내지 7.1로 조절하여 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the neutralization step is performed by mixing 1N hydrochloric acid into the mixture prepared through the succinic acid mixing step to adjust the pH of the mixture to 6.9 to 7.1.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 원심분리단계는 4500 내지 5500rpm의 속도로 8 내지 12분 동안 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the centrifugation step is performed at a speed of 4500 to 5500 rpm for 8 to 12 minutes.

본 발명에 따른 쌀세정수를 이용한 전분의 제조방법은 유화 안정성 및 냉해동 안정성이 월등하게 향상된 전분을 제조하는 탁월한 효과를 나타낸다.The method for producing starch using rice washing water according to the present invention exhibits an excellent effect of producing starch with significantly improved emulsification stability and freeze-thaw stability.

도 1은 본 발명의 일 실시예에 따른 쌀세정수를 이용한 전분의 제조방법을 나타낸 순서도이다.
도 2는 본 발명의 다른 실시예에 따른 쌀세정수를 이용한 전분의 제조방법을 나타낸 순서도이다.
도 3은 실시예 1 내지 4를 통해 제조된 전분의 외관을 촬영하여 나타낸 사진이다.
도 4는 세정수분말 및 세정수전분으로 제조한 OSA전분, 어닐링 OSA전분을 제조한 유화액의 점도를 측정하여 나타낸 그래프이다.
도 5는 세정수 분말 및 OSA전분을 함유한 찐만두용 만두피의 냉해동안정성 측정결과를 나타낸 그래프이다.
Figure 1 is a flow chart showing a method for manufacturing starch using rice washing water according to one embodiment of the present invention.
Figure 2 is a flow chart showing a method for manufacturing starch using rice washing water according to another embodiment of the present invention.
Figure 3 is a photograph showing the appearance of starch manufactured through Examples 1 to 4.
Figure 4 is a graph showing the viscosity of an emulsion manufactured from annealed OSA starch and annealed OSA starch manufactured from washed water powder and washed water starch.
Figure 5 is a graph showing the results of measuring the cold-thaw stability of dumpling skins for steamed dumplings containing washing water powder and OSA starch.

이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, preferred embodiments of the present invention and the properties of each component will be described in detail. However, this is intended to be a detailed description to enable a person having ordinary skill in the art to which the present invention pertains to easily carry out the invention, and does not mean that the technical idea and scope of the present invention are limited thereby.

본 발명에 따른 쌀세정수를 이용한 전분의 제조방법은 쌀세정수에서 전분을 회수하는 전분회수단계(S101), 상기 전분회수단계(S101)를 통해 회수된 전분에 증류수를 혼합하는 증류수혼합단계(S103), 상기 증류수혼합단계(S103)를 통해 제조된 혼합물에 무수옥테닐 호박산과 수산화나트륨을 혼합하는 호박산혼합단계(S105), 상기 호박산혼합단계(S105)를 통해 제조된 혼합물을 중화하는 중화단계(S107), 상기 중화단계(S107)를 통해 중화된 혼합물을 원심분리하는 원심분리단계(S109) 및 상기 원심분리단계(S109)를 통해 분리된 전분을 세척한 후에 열풍건조하는 세척건조단계(S111)로 이루어진다.The method for manufacturing starch using rice washing water according to the present invention comprises a starch recovery step (S101) of recovering starch from rice washing water, a distilled water mixing step (S103) of mixing distilled water with the starch recovered through the starch recovery step (S101), a succinic acid mixing step (S105) of mixing anhydrous octenyl succinic acid and sodium hydroxide with the mixture prepared through the distilled water mixing step (S103), a neutralization step (S107) of neutralizing the mixture prepared through the succinic acid mixing step (S105), a centrifugation step (S109) of centrifuging the mixture neutralized through the neutralization step (S107), and a washing and drying step (S111) of washing the starch separated through the centrifugation step (S109) and then drying it with hot air.

상기 전분회수단계(S101)는 쌀세정수에서 전분을 회수하는 단계로, 쌀세정수는 백미에 2배수의 물을 부어 2회 세척하는 과정으로 제조된다.The above starch recovery step (S101) is a step for recovering starch from rice washing water. The rice washing water is manufactured by pouring twice as much water into white rice and washing it twice.

상기의 과정에서 씻어낸 백미 낟알은 0.2% 수산화나트륨용액과 함께 분쇄하여 알칼리 침지법으로 전분을 분리하였고 백미 정제전분이라고 명명하였다.The white rice grains washed in the above process were ground with a 0.2% sodium hydroxide solution and the starch was separated using an alkaline steeping method, and named white rice refined starch.

상기 전분의 회수는 쌀세정수를 35℃의 온도에서 진공농축하여 원심분리 한후 침전물을 상온건조하여 세정수 농축분말을 제조하거나, 쌀세정수를 농축과정 없이 원심분리한 후 침전물을 상온건조하여 침전분말을 제조하거나, 쌀세정수를 원심분리한 후에 침전물을 회수하고, 회수된 침전물을 질량농도가 0.2%인 수산화나트륨수용액으로 정제한 후에 1N 염산용액으로 중화하고 세척 및 건조하여 이루어질 수있는데, 마지막 방법을 이용하는 것이 가장 바람직하다.The above recovery of starch can be accomplished by vacuum concentrating rice washing water at a temperature of 35°C, centrifuging the resulting solution, and drying the precipitate at room temperature to produce concentrated washing water powder, or by centrifuging the rice washing water without a concentration process, then drying the precipitate at room temperature to produce precipitate powder, or by centrifuging the rice washing water, recovering the precipitate, purifying the recovered precipitate with a sodium hydroxide aqueous solution having a mass concentration of 0.2%, neutralizing it with a 1 N hydrochloric acid solution, washing it, and drying it, but the use of the last method is most preferable.

상기 증류수혼합단계(S103)는 상기 전분회수단계(S101)를 통해 회수된 전분에 증류수를 혼합하는 단계로, 상기 전분회수단계(S101)를 통해 제조된 전분 100 중량부에 증류수 180 내지 300 중량부를 혼합하여 이루어진다.The above distilled water mixing step (S103) is a step of mixing distilled water with the starch recovered through the starch recovery step (S101), and is performed by mixing 180 to 300 parts by weight of distilled water with 100 parts by weight of the starch manufactured through the starch recovery step (S101).

상기 증류수혼합단계(S103)에서 증류수의 혼합량이 180 중량부 미만이거나 300 중량부를 초과하게 되면 전분제조공정의 효율성이 저하된다.In the above distilled water mixing step (S103), if the mixing amount of distilled water is less than 180 parts by weight or exceeds 300 parts by weight, the efficiency of the starch manufacturing process is reduced.

상기 호박산혼합단계(S105)는 상기 증류수혼합단계(S103)를 통해 제조된 혼합물에 무수옥테닐 호박산(octenyl succinic anhydride, OSA)과 수산화나트륨을 혼합하는 단계로, 상기 증류수혼합단계(S103)를 통해 제조된 혼합물에 함유된 전분 100 중량부 대비 무수옥테닐 호박산 2 내지 4 중량부를 혼합하고, 수산화나트륨을 혼합하여 혼합물의 pH를 8 내지 9로 유지한 상태에서 5 내지 7시간 동안 반응하는 과정으로 이루어진다.The above succinic acid mixing step (S105) is a step of mixing anhydrous octenyl succinic anhydride (OSA) and sodium hydroxide with the mixture prepared through the distilled water mixing step (S103). The step comprises mixing 2 to 4 parts by weight of anhydrous octenyl succinic anhydride relative to 100 parts by weight of starch contained in the mixture prepared through the distilled water mixing step (S103), mixing in sodium hydroxide, and reacting the mixture for 5 to 7 hours while maintaining the pH of the mixture at 8 to 9.

상기의 과정을 통해 호박산되 반응하여 제조되는 전분은 유화 안정성과 냉해동 안정성이 월등하게 향상된다.The starch manufactured by the above process through the succinic acid reaction has significantly improved emulsion stability and freeze-thaw stability.

상기 중화단계(S107)는 상기 호박산혼합단계(S105)를 통해 제조된 혼합물을 중화하는 단계로, 상기 호박산혼합단계(S105)를 통해 제조된 혼합물에 1N의 염산을 혼합하여 혼합물의 pH를 6.9 내지 7.1로 조절하여 이루어진다.The neutralization step (S107) above is a step of neutralizing the mixture manufactured through the succinic acid mixing step (S105), and is performed by mixing 1N hydrochloric acid into the mixture manufactured through the succinic acid mixing step (S105) to adjust the pH of the mixture to 6.9 to 7.1.

상기의 과정을 통해 중화된 혼합물에 함유된 전분은 중화처리되어 식품첨가용 전분으로 활용할 수 있다.Through the above process, the starch contained in the neutralized mixture can be neutralized and used as starch for food additives.

상기 원심분리단계(S109)는 상기 중화단계(S107)를 통해 중화된 혼합물을 원심분리하는 단계로, 상기 중화단계(S107)를 통해 중화된 혼합물을 원심분리기에 투입하고 4500 내지 5500rpm의 속도로 8 내지 12분 동안 원심분리하는 과정으로 이루어진다.The above centrifugation step (S109) is a step of centrifuging the mixture neutralized through the neutralization step (S107), and is comprised of a process of putting the mixture neutralized through the neutralization step (S107) into a centrifuge and centrifuging it at a speed of 4,500 to 5,500 rpm for 8 to 12 minutes.

상기의 과정을 통해 혼합물로부터 전분이 분리될 수 있는데, 상기 원심분리단계(S109)의 속도가 4500rpm미만이거나 원심분리 시간이 8분 미만이면 분리되는 전분의 수율이 낮아지며, 상기 원심분리단계(S109)의 속도가 5500rpm을 초과하거나 원심분리시간이 12분을 초과하게 되면 불필요하게 에너지를 낭비하게 되는 것으로 바람직하지 못하다.Through the above process, starch can be separated from the mixture, but if the speed of the centrifugation step (S109) is less than 4,500 rpm or the centrifugation time is less than 8 minutes, the yield of separated starch is low, and if the speed of the centrifugation step (S109) exceeds 5,500 rpm or the centrifugation time exceeds 12 minutes, energy is unnecessarily wasted, which is not desirable.

상기 세척건조단계(S111)는 상기 원심분리단계(S109)를 통해 분리된 전분을 세척한 후에 열풍건조하는 단계로, 상기 원심분리단계(S109)를 통해 분리된 전분을 증류수로 세척하여 이물질을 제거한 후에, 50 내지 70℃의 열풍을 이용하여 건조하는 과정으로 이루어진다.The above washing and drying step (S111) is a step of washing the starch separated through the centrifugation step (S109) and then drying it with hot air. The step is comprised of washing the starch separated through the centrifugation step (S109) with distilled water to remove foreign substances, and then drying it using hot air at 50 to 70°C.

또한, 상기 증류수혼합단계(S103)와 상기 호박산혼합단계(S105) 사이에는 상기 증류수혼합단계(S103)를 통해 제조된 혼합물을 어닐링하는 어닐링단계(S104)가 더 진행될 수 있으며, 상기 어닐링단계(S104)는 40 내지 50℃의 온도에서 20 내지 30시간 동안 이루어지는 것이 바람직하다.In addition, an annealing step (S104) of annealing the mixture manufactured through the distilled water mixing step (S103) may be further performed between the distilled water mixing step (S103) and the succinic acid mixing step (S105), and it is preferable that the annealing step (S104) be performed at a temperature of 40 to 50°C for 20 to 30 hours.

상기의 온도와 시간동안 진행되는 어닐링 과정을 거치면, 유화 안정성 및 냉해동 안정성이 더욱 향상된 전분이 제공된다.By performing an annealing process at the above temperature and time, starch with improved emulsion stability and freeze-thaw stability is provided.

이하에서는, 본 발명에 따른 쌀세정수를 이용한 전분의 제조방법 및 그 제조방법으로 제조된 전분의 물성을 실시예를 들어 설명하기로 한다.Hereinafter, a method for manufacturing starch using rice washing water according to the present invention and the properties of starch manufactured by the method will be described with examples.

<실시예 1> 백미 정제전분의 제조<Example 1> Production of refined white rice starch

씻어낸 백미 낟알을 질량농도가 0.2%인 수산화나트륨수용액과 분쇄하여 알칼리 침지법으로 전분을 분리하여 백미 정제전분을 제조하였다.Washed white rice grains were ground with a 0.2% mass concentration sodium hydroxide aqueous solution and starch was separated using an alkaline steeping method to produce refined white rice starch.

<실시예 2> 세정수 녹축분말의 제조<Example 2> Production of green powder for washing water

백미에 2배수의 물을 부어 2회 세척한 후, 세척에 사용된 물을 모아 쌀세정수를 제조하고, 상기 쌀세정수를 35℃에서 진공농축하고 원심분리한 후에 침전물을 상온건조하여 세정수 농축분말을 제조하였다.After washing white rice twice with twice the amount of water, the water used for washing was collected to produce rice washing water. The rice washing water was vacuum concentrated at 35°C, centrifuged, and the precipitate was dried at room temperature to produce concentrated washing water powder.

<실시예 3> 세정수 침전분말의 제조<Example 3> Production of precipitated powder from washing water

백미에 2배수의 물을 부어 2회 세척한 후, 세척에 사용된 물을 모아 쌀세정수를 제조하고, 쌀세정수를 원심분리한 후 침전물을 상온건조하여 세정수 침전분말을 제조하였다.After washing the white rice twice with twice the amount of water, the water used for washing was collected to produce rice washing water. The rice washing water was centrifuged and the sediment was dried at room temperature to produce washing water precipitate powder.

<실시예 4> 세정수 정제전분의 제조<Example 4> Production of purified starch from washing water

백미에 2배수의 물을 부어 2회 세척한 후, 세척에 사용된 물을 모아 쌀세정수를 제조하고, 제조된 쌀세정수를 원심분리하여 침전물을 질량농도가 0.2%인 수산화나트륨수용액으로 정제한 후에, 1N 염산용액으로 중화(pH 7.0)시킨 후 증류수로 씻어내고 침전물을 상온건조하여 세정수 정제전분을 제조하였다.White rice was washed twice with twice the amount of water, the water used for washing was collected to prepare rice washing water, the prepared rice washing water was centrifuged, and the precipitate was purified with a 0.2% mass concentration sodium hydroxide aqueous solution, neutralized (pH 7.0) with a 1 N hydrochloric acid solution, washed with distilled water, and the precipitate was dried at room temperature to prepare washed water purified starch.

<실시예 5> 백미 정제전분 OSA 제조<Example 5> Manufacturing of OSA from refined white rice starch

상기 실시예 1을 통해 제조된 백미 정제전분 50g에 증류수를 120mL을 가한 후 1N NaOH를 사용하여 pH 8.5를 유지하면서 OSA 용액을 전분 무게의 3%가 되도록 첨가하여 6시간 반응 후 1N HCl을 사용하여 pH 7.0으로 중화시키고 원심분리기로 5,000rpm의 속도로 10분 동안 침전시킨 후 증류수로 세척 및 열풍건조하여 전분을 제조하였다.(백미 정제전분-OSA)120 mL of distilled water was added to 50 g of the white rice refined starch manufactured through the above Example 1, and then 1 N NaOH was used to maintain the pH at 8.5, and OSA solution was added to 3% of the starch weight, and after 6 hours of reaction, the solution was neutralized to pH 7.0 using 1 N HCl, and precipitated in a centrifuge at a speed of 5,000 rpm for 10 minutes, and then washed with distilled water and dried with hot air to manufacture starch. (White rice refined starch-OSA)

<실시예 6> 세정수 정제전분 OSA 제조<Example 6> Manufacturing of OSA from purified starch using washing water

상기 실시예 5와 동일하게 진행하되 상기 실시예 2를 통해 제조된 세정수 정제전분을 사용하여 전분을 제조하였다.(세정수 정제전분-OSA)The same procedure as in Example 5 was followed, but starch was manufactured using the purified starch from the washing water manufactured through Example 2. (Refined starch from washing water-OSA)

<실시예 7> 세정수 침전분말 OSA 제조<Example 7> Manufacturing of OSA from precipitated powder of washing water

상기 실시예 5와 동일하게 진행하되 상기 실시예 3을 통해 제조된 세정수 정제전분을 사용하여 전분을 제조하였다.(세정수 침전분말-OSA)The same procedure as in Example 5 was followed, but starch was manufactured using the purified starch from the washing water produced in Example 3. (Washing water precipitated powder-OSA)

<실시예 8> 세정수 농축분말 OSA 제조<Example 8> Manufacturing of OSA concentrated powder from washing water

상기 실시예 5와 동일하게 진행하되 상기 실시예 4를 통해 제조된 세정수 정제전분을 사용하여 전분을 제조하였다.(세정수 농축분말-OSA)The same procedure as in Example 5 was followed, but starch was manufactured using the purified starch from the washing water produced in Example 4. (Concentrated washing water powder-OSA)

<실시예 9> 어닐링 전분(40℃) 제조<Example 9> Manufacturing of annealed starch (40°C)

상기 실시예 3을 통해 제조된 세정수 정제전분 50g을 40℃의 온도에서 24시간 동안 어닐링하여 어닐링전분(40℃)을 제조하였다.Annealed starch (40°C) was produced by annealing 50 g of the purified starch produced in Example 3 above at a temperature of 40°C for 24 hours.

<실시예 10> 어닐링 전분(50℃) 제조<Example 10> Manufacturing of annealed starch (50°C)

상기 실시예 3을 통해 제조된 세정수 정제전분 50g을 50℃의 온도에서 24시간 동안 어닐링하여 어닐링전분(50℃)을 제조하였다.50 g of the purified starch produced in Example 3 above was annealed at 50°C for 24 hours to produce annealed starch (50°C).

<실시예 11> 어닐링 OSA 전분(40℃) 제조<Example 11> Manufacturing of annealed OSA starch (40°C)

상기 실시예 3을 통해 제조된 세정수 정제전분 50g에 증류수를 120mL을 가한 후 40℃의 온도에서 24시간 동안 어닐링하고, 어닐링된 혼합물을 1N NaOH를 사용하여 pH 8.5를 유지하면서 OSA 용액을 전분 무게의 3%가 되도록 첨가하여 6시간 반응 후 1N HCl을 사용하여 pH 7.0으로 중화시키고 원심분리기로 5,000rpm의 속도로 10분 동안 침전시킨 후 증류수로 세척 및 열풍건조하여 전분을 제조하였다.{어닐링 OSA 전분(40℃)}120 mL of distilled water was added to 50 g of the purified starch manufactured through the above Example 3, and then annealed at a temperature of 40°C for 24 hours. The annealed mixture was maintained at pH 8.5 using 1 N NaOH, and an OSA solution was added to an amount of 3% of the starch weight, and after 6 hours of reaction, the mixture was neutralized to pH 7.0 using 1 N HCl, and precipitated using a centrifuge at a speed of 5,000 rpm for 10 minutes, washed with distilled water, and dried with hot air to manufacture starch. {Annealed OSA starch (40°C)}

<실시예 12> 어닐링 OSA 전분(50℃) 제조<Example 12> Manufacturing of annealed OSA starch (50°C)

상기 실시예 11과 동일하게 진행하되 50℃로 어닐링하여 전분을 제조하였다.{어닐링 OSA 전분(50℃)}The same procedure as in Example 11 was followed, but starch was manufactured by annealing at 50°C. {Annealed OSA starch (50°C)}

상기 실시예 1 내지 12를 통해 제조된 전분의 물성을 측정하여 아래에 나타내었다.The properties of the starch manufactured through the above Examples 1 to 12 were measured and are shown below.

*세정수 분말 및 정제된 전분의 색도 측정*Color measurement of washing powder and refined starch

세정수에서 분리한 분말 및 정제전분의 색도는 분광측색계(CM-5, Minolta, Japan)를 사용하여 명도(L), 적색도(a), 황색도(b)를 측정하여 아래 표 1 및 도 3에 나타내었다.The color of the powder and refined starch separated from the washing water was measured using a spectrophotometer (CM-5, Minolta, Japan) in terms of lightness (L), redness (a), and yellowness (b), and is shown in Table 1 and Figure 3 below.

<표 1><Table 1>

상기 표 1 및 아래 도 3에 나타낸 것처럼, 백미 및 쌀 세정수 시료의 색도를 측정한 결과 백미 정제전분, 세정수 정제전분, 세정수 침전분말, 세정수 농축분말의 L, a, b 값은 91.56~99.44, 0.16~0.53, 1.02~10.69였다. 시료의 정제도가 높을수록 명도가 높아 흰색을 띄었고 정제도가 낮은 분말일수록 황색도가 증가하였다.As shown in Table 1 above and Fig. 3 below, the L, a, and b values of white rice refined starch, washed water refined starch, washed water precipitate powder, and washed water concentrated powder were 91.56 to 99.44, 0.16 to 0.53, and 1.02 to 10.69, respectively, when the color of white rice and rice washed water samples was measured. The higher the degree of purification of the sample, the higher the brightness and the whiter the color appeared, and the lower the degree of purification, the higher the yellowness.

*백미 및 세정수로부터 분리한 분말 및 전분의 일반성분 및 전분 함량*General composition and starch content of powder and starch separated from white rice and washed water

백미 및 세정수에서 정제한 전분의 일반성분은 AACCI(2012)에 따라 조회분 함량, 조단백질 및 조지방을 분석하였다. 조회분은 550℃에서 직접회화법으로 측정하였고, 조단백질은 Kjeldahl법을 이용한 분석기를, 조지방은 Soxhlet 추출법을 이용한 자동추출장치를 사용하였다. 백미 및 세정수에서 분리한 시료의 총전분함량은 전분 100 mg(db)에 총전분 분석용 키트(Megazymes Pty)를 사용하여 분석하여 아래 표 2에 나타내었다.The general composition of starch purified from white rice and washing water was analyzed for ash content, crude protein, and crude fat according to AACCI (2012). Ash content was measured by direct ash method at 550℃, crude protein was analyzed using an analyzer using the Kjeldahl method, and crude fat was analyzed using an automatic extraction device using the Soxhlet extraction method. The total starch content of the sample separated from white rice and washing water was analyzed using a total starch analysis kit (Megazymes Pty) at 100 mg (db) of starch, and is shown in Table 2 below.

<표 2><Table 2>

상기 표 2에 나타낸 것처럼, 쌀세정수를 식품소재로써 활용가능성을 확인하기 위해 세정수로부터 분말과 전분을 분리하고 백미에서 분리한 전분과 특성을 비교하였다. 정제하지 않은 세정수 침전분말은 도정과정에서 낟알표면에 붙은 쌀겨와 백미의 가용성 물질들이 함유되어 있고, 세정수 정제전분은 세정수 침전분말을 알칼리 정제하여 얻은 전분이며, 백미 정제전분은 백미로부터 알칼리정제하여 얻어진 전분이다. 각 시료의 일반성분은 상기 표 1과 같이 수분함량 8.56~11.17%, 회분 0.66~12.02%, 조단백질 0.50~31.91%, 조지질 0.10~10.84%, 총전분 63.19~93.74% 였다. 세정수 침전분말과 농축분말은 백미 정제전분과 세정수 정제전분에 비해 조단백질, 조지질, 회분 함량은 높고 총전분 함량은 낮았으며, 세정수 정제전분은 백미 정제전분보다 단백질 함량은 높고 총전분 함량은 낮았다.As shown in Table 2 above, in order to confirm the possibility of utilizing rice washing water as a food material, the powder and starch were separated from the washing water, and the characteristics were compared with the starch separated from white rice. The unrefined washing water precipitate powder contains rice bran attached to the surface of the grains and soluble substances of white rice during the milling process, the washing water refined starch is starch obtained by alkali refining the washing water precipitate powder, and the white rice refined starch is starch obtained by alkali refining white rice. The general components of each sample were as shown in Table 1 above: moisture content 8.56~11.17%, ash 0.66~12.02%, crude protein 0.50~31.91%, crude lipid 0.10~10.84%, and total starch 63.19~93.74%. Compared to white rice refined starch and washed water refined starch, the washed water precipitate powder and concentrated powder had higher crude protein, crude lipid, and ash contents and lower total starch contents. Wash water refined starch had higher protein content and lower total starch content than white rice refined starch.

*이화학적 특성*Physicochemical properties

백미 및 세정수에서 분리한 시료 및 OSA전분의 물결합능력은 Medcalf DG & Gilles KA(1965)의 방법에 따라 측정하였다. 전분 0.5 g(db)에 증류수 20 mL을 가하여 상온에서 1시간동안 교반시킨 후 원심분리기로 5,000 rpm에서 30분간 원심분리하였다. 상층액을 제거하고 침전물의 무게를 측정하여 처음 시료와의 중량비로부터 계산하여 물결합능력(%)을 나타냈다.The water binding capacity of the sample separated from white rice and washing water and OSA starch was measured according to the method of Medcalf DG & Gilles KA (1965). 20 mL of distilled water was added to 0.5 g (db) of starch, stirred at room temperature for 1 hour, and centrifuged at 5,000 rpm for 30 minutes. The supernatant was removed, and the weight of the sediment was measured, and the water binding capacity (%) was calculated from the weight ratio with the original sample.

팽윤력과 용해도는 80℃에서 측정하였다. 원심분리관에 전분 0.5g(db)와 증류수 20 mL을 넣어 80℃에서 30분간 교반하고 얼음물에 넣어 냉각시킨 후 8,000 rpm에서 30분간 원심분리하였다. 상등액의 건조무게와 침전물의 무게를 측정하여 팽윤력과 용해도를 계산하였다.Swelling capacity and solubility were measured at 80℃. 0.5 g (db) of starch and 20 mL of distilled water were placed in a centrifuge tube, stirred at 80℃ for 30 minutes, cooled in ice water, and centrifuged at 8,000 rpm for 30 minutes. The dry weight of the supernatant and the weight of the sediment were measured to calculate the swelling capacity and solubility.

<표 3><Table 3>

상기 표 3에 나타낸 것처럼, 백미 및 세정수에서 분리한 분말 및 전분과 그 시료로 제조한 OSA전분의 물결합능력 및 팽윤력, 용해도를 측정한 결과는 221.69~450.48%. 5.37~38.91, 4.73~20.92% 였다. 백미 정제전분에 비해 세정수 정제전분은 432.59%로 매우 높은 물결합능력을 나타냈고, 세정수에서 분리한 전분에 비해 정제하지 않은 분말인 세정수 침전분말과 세정수 농축분말의 물결합능력은 유의적으로 감소하였다. OSA 에스터화로 제조된 시료들은 OSA 처리를 하지 않은 전분들과 유사한 경향을 보였으며, 정제전분인 백미정제전분-OSA와 세정수 정제전분-OSA의 경우 OSA 처리가 물결합능력을 증가시켰음을 알 수 있다.As shown in Table 3 above, the water-binding capacity, swelling power, and solubility of the powder and starch separated from white rice and washing water and the OSA starch manufactured with the samples were 221.69–450.48%, 5.37–38.91, and 4.73–20.92%, respectively. Compared to white rice refined starch, the washed water refined starch showed a very high water-binding capacity of 432.59%, and the water-binding capacity of the unrefined powder washed water precipitated powder and washed water concentrated powder significantly decreased compared to the starch separated from the washed water. The samples manufactured by OSA esterification showed a similar tendency to the starches that were not treated with OSA, and it could be seen that the water-binding capacity of the refined starches, white rice refined starch-OSA and washed water refined starch-OSA, increased.

전분 및 OSA전분의 팽윤력을 측정한 결과, OSA를 처리하지 않은 전분 및 분말은 물결합 능력의 결과와 유사하게 백미 정제전분에 비해 세정수 정제전분이 16.97%로 팽윤력이 유의적으로 높았고, 세정수 정제전분에 비해 세정수 침전분말과 농축분말의 팽윤력은 유의적으로 감소하였다. OSA를 처리한 경우 무처리군에 비해 팽윤력이 증가하였으며 특히 백미정제전분-OSA는 무처리군에 비해 가장 크게 증가하여 세정수 정제전분-OSA보다 높은 값은 나타냈다. 용해도는 OSA 무처리군과 처리군에서 물결합능력과 유사한 경향을 나타냈다.As a result of measuring the swelling power of starch and OSA starch, the starch and powder without OSA treatment had a significantly higher swelling power of washed water refined starch than white rice refined starch at 16.97%, similar to the results of water-binding capacity, and the swelling power of the washed water precipitated powder and concentrated powder significantly decreased compared to the washed water refined starch. When treated with OSA, the swelling power increased compared to the untreated group, and in particular, white rice refined starch-OSA increased the most compared to the untreated group, showing a higher value than the washed water refined starch-OSA. Solubility showed a similar trend to the water-binding capacity in the untreated and OSA treated groups.

본 발명에서 백미에서 분리정제한 전분과 세정수에서 정제한 전분이 물결합능력, 팽윤력과 용해도에 차이가 나는 것을 보았을 때 배유부분의 전분과 쌀겨와 백미 표면에서 세정수로 이행되는 전분은 입자크기와 구조에 차이가 있을 것으로 추측하였다. 세정수에서 분리정제한 전분과 정제하지 않은 분말의 특성치에 차이가 있는 이유는 세정수에서 유래한 단백질, 지질, 회분 등이 전분입자의 수화와 팽윤을 억제하기 때문이다.In the present invention, when it was observed that starch purified from white rice and starch purified from washing water had differences in water binding capacity, swelling capacity, and solubility, it was presumed that starch in the endosperm portion and starch transferred from rice bran and the surface of white rice into the washing water had differences in particle size and structure. The reason for the difference in characteristics between starch purified from washing water and unrefined powder is that proteins, lipids, ash, etc. derived from washing water inhibit hydration and swelling of starch particles.

*신속점도측정기에 의한 호화 특성 측정*Measurement of gelatinization properties by rapid viscosity meter

전분 및 OSA전분 호화액의 온도에 따른 점도변화는 신속점도측정기(RVA 4500, Perten, Hgersten, Sweden)를 이용하여 측정하였다. 알루미늄 용기에 시료(3 g, 12% 수분함량기준)을 중류수 25 mL로 잘 분산시키고 50℃에서 1분간, 95℃까지 3.12분간 가열, 95℃에서 2.92분간 유지, 50℃까지 3.97분간 냉각, 50℃에서 2분간 유지하면서 점도를 측정하였다. 측정한 데이터로부터 호화개시온도(℃), 피크타임(분), 최고점도(peak viscosity, P), 최저점도(trough viscosity, T), 최종점도(final viscosity, F), 치반점도(setback viscosity, F-T), 강하점도(breakdown viscosity, P-T)를 구하였다. The viscosity change of starch and OSA starch gelatin solution according to temperature was measured using a rapid viscosity meter (RVA 4500, Perten, H The viscosity was measured using a gelatinization initiation temperature (℃), peak time (min), peak viscosity (P), trough viscosity (T), final viscosity (F), setback viscosity (FT), and breakdown viscosity (PT) were measured. The sample (3 g, based on 12% moisture content) was well dispersed in 25 mL of distilled water in an aluminum container, and the viscosity was measured at 50°C for 1 minute, heated to 95°C for 3.12 minutes, maintained at 95°C for 2.92 minutes, cooled to 50°C for 3.97 minutes, and maintained at 50°C for 2 minutes. From the measured data, the gelatinization initiation temperature (℃), peak time (min), peak viscosity (P), trough viscosity (T), final viscosity (F), setback viscosity (FT), and breakdown viscosity (PT) were obtained.

<표 4><Table 4>

상기 표 4에 나타낸 것처럼, 세정수에서 분리한 전분 및 분말의 호화특성을 조사하기위해 신속점도측정계(RVA)로 측정하였는데, 백미에서 분리한 정제전분의 호화 특성은 호화개시온도, 피크타임, 최고점도, 최저점도, 최종점도, 치반점도, 강하점도를 분석한 결과 74.08℃, 6.10분, 3645 cP, 2643 cP, 4268 cP, 1626 cP, 1003 cP였다. 세정수 정제전분은 호화개시온도가 약간 증가하였으나 점도는 낮아졌다. 세정수 침전분말은 호화개시온도와 피크타임이 93.63℃와 7.00분으로 호화온도와 피크타임이 증가하였고 세정수 정제전분보다 높은 점도를 유지했으나 세정수 농축분말은 호화온도가 측정되지 않았고 피크타임은 6.07분이으로 일반적인 전분의 호화패턴을 보이지 않아 농축과정에서 전분이 손상되었다고 판단된다.As shown in Table 4 above, the gelatinization characteristics of the starch and powder separated from the washing water were measured using a rapid viscosity analyzer (RVA). The gelatinization characteristics of the refined starch separated from white rice were analyzed in terms of gelatinization initiation temperature, peak time, highest viscosity, lowest viscosity, final viscosity, settling viscosity, and drop-off viscosity, and were 74.08℃, 6.10 min, 3645 cP, 2643 cP, 4268 cP, 1626 cP, and 1003 cP. The gelatinization initiation temperature of the refined starch in the washing water slightly increased, but the viscosity decreased. The gelatinization temperature and peak time of the washed water precipitated powder were 93.63℃ and 7.00 minutes, respectively, which increased the gelatinization temperature and peak time and maintained a higher viscosity than the washed water purified starch. However, the washed water concentrated powder did not have a measured gelatinization temperature and its peak time was 6.07 minutes, which did not show the general starch gelatinization pattern, suggesting that the starch was damaged during the concentration process.

정제된 전분으로 제조한 백미정제전분-OSA와 세정수 정제전분-OSA는 각각의 무처리 시료보다 호화온도와 피크타임이 감소하였으나 점도는 모두 증가하였으며 세정수 침전분말-OSA는 무처리군과 유사한 호화양상을 나타냈고 세정수 농축분말-OSA는 무처리군보다 점도가 감소하였다.White rice refined starch-OSA and washed water refined starch-OSA manufactured from refined starch showed decreased gelatinization temperature and peak time compared to the untreated sample, but increased viscosity in both samples. Washed water precipitate powder-OSA showed a gelatinization pattern similar to the untreated group, and washed water concentrated powder-OSA showed a decreased viscosity compared to the untreated group.

*OSA 치환도 측정*OSA substitution degree measurement

OSA전분 및 분말의 옥테닐 석시닐기의 치환도는 다음과 같은 방법으로 측정하였다. 전분 5 g을 삼각플라스크에 넣고 50 mL의 증류수를 가하여 잘 혼합한 다음 0.5 N NaOH 용액 25 mL를 가하였다. 마그네틱 바를 이용하여 상온에서 24시간동안 교반한 후 치환된 옥테닐석실산이 NaOH와 반응하고 남은 알칼리 양을 0.5 N HCl로 적정하여 치환도를 계산하였다.The degree of substitution of octenyl succinyl groups in OSA starch and powder was measured by the following method. 5 g of starch was placed in a triangular flask, 50 mL of distilled water was added, and mixed well. Then, 25 mL of 0.5 N NaOH solution was added. After stirring for 24 hours at room temperature using a magnetic bar, the substituted octenyl succinic acid reacted with NaOH, and the remaining amount of alkali was titrated with 0.5 N HCl to calculate the degree of substitution.

*유지흡착력(Oil absorption capacity)*Oil absorption capacity

유지흡착력을 측정하기 위해 OSA 전분 0.5 g과 카놀라유 15 mL를 볼텍스믹서로 30초간 혼합하여 30분간 정치시킨 후 2730×g에서 20분간 원심분리하였고 상등액은 버린 후 침전물의 무게를 측정한 후 아래 식으로 유지흡착력을 계산하였다.To measure the retention capacity, 0.5 g of OSA starch and 15 mL of canola oil were mixed for 30 seconds using a vortex mixer, allowed to settle for 30 minutes, and centrifuged at 2730×g for 20 minutes. The supernatant was discarded, and the weight of the sediment was measured. The retention capacity was then calculated using the following equation.

Oil absorption capacity (%) = [Precipitated starch weight (g) - Initial starch weight (g)] × 100 / Starch weight (g)Oil absorption capacity (%) = [Precipitated starch weight (g) - Initial starch weight (g)] × 100 / Starch weight (g)

<표 5><Table 5>

상기 표 5에 나타낸 것처럼, 세정수에서 분리한 시료로 OSA전분을 제조한 후 OSA 치환도를 측정한 결과 0.014~0.088 이었고, 세정수 전분과 분말로 제조한 3종의 OSA전분들은 백미 정제전분-OSA보다 치환도가 높았다. 특히 세정수를 농축하여 분말화한 세정수 농축분말의 경우 OSA치환도가 가장 높은 값을 나타냈다.As shown in Table 5 above, the OSA substitution degree was measured after manufacturing OSA starch from the sample separated from the washing water, and the result was 0.014~0.088, and the three types of OSA starches manufactured from washing water starch and powder had higher substitution degrees than white rice refined starch-OSA. In particular, the washing water concentrated powder, which was made by concentrating the washing water and turning it into powder, showed the highest value of OSA substitution degree.

OSA 처리를 하지 않은 전분과 OSA전분의 유지흡착력을 측정한 결과 110.07~129.09%였다. OSA 처리를 하지 않은 경우 백미에서 분리한 백미정제전분보다 세정수에서 분리한 세정수 침전분말과 농축분말의 유지흡착력이 높았다. 세정수 침전분말과 농축분말은 다른 시료에 비해 지질함량이 높게 측정되었고, 여기에 함유된 지용성 성분이 영향을 주었다고 판단하였다. 또한 각 시료로 제조된 OSA전분의 경우 OSA 처리에 의해 유지흡착력이 증가되어 세정수 시료로 제조한 OSA 전분은 유화안정제로써 활용가능성이 높다고 판단된다.The results of measuring the retention capacity of starch without OSA treatment and OSA starch were 110.07~129.09%. In the case of no OSA treatment, the retention capacity of the washed water precipitated powder and concentrated powder separated from the washed water was higher than that of the white rice refined starch separated from the white rice. The washed water precipitated powder and concentrated powder were measured to have a higher lipid content than the other samples, and it was determined that the fat-soluble components contained therein had an effect. In addition, in the case of the OSA starch manufactured with each sample, the retention capacity increased by the OSA treatment, and it was determined that the OSA starch manufactured with the washed water sample has a high possibility of being utilized as an emulsifying stabilizer.

*세정수분말 및 세정수전분으로 제조한 OSA전분을 함유한 유화액의 제조 *Manufacture of emulsion containing OSA starch manufactured from detergent powder and detergent starch

유화액은 50 g 카놀라유, 50 g continuous phase를 혼합하여 제조하였다. continuous phase 50 g은 1 g 세정수 분말 또는 전분, 0.02 g 잔탄검, 0.01 g 아지드화 나트륨, 48.97 g 물로 구성되었고, OSA 전분은 미리 50℃에서 분산시켰고 잔탄검은 48시간동안 교반하여 균질화하였다. 카놀라유와 continuous phase를 혼합하여 1~3분간 고속 호모게나이저로 균질화 한 후 sonicator로 amplitude 40%에서 1 분간 처리하여 유화액을 제조하였다.The emulsion was prepared by mixing 50 g of canola oil and 50 g of continuous phase. The 50 g of continuous phase consisted of 1 g of washed water powder or starch, 0.02 g of xanthan gum, 0.01 g of sodium azide, and 48.97 g of water. The OSA starch was dispersed in advance at 50°C, and the xanthan gum was homogenized by stirring for 48 hours. The canola oil and continuous phase were mixed, homogenized with a high-speed homogenizer for 1 to 3 minutes, and then sonicated with a sonicator at amplitude 40% for 1 minute to prepare an emulsion.

-유화액의 점도 및 안정성 측정-Measurement of viscosity and stability of emulsion

유화액의 점도는 Brookfield 점도계를 사용하여 측정하였고, 10 mL 메스실린더에 유화액을 채우고 저장하면서 분리되는 부피를 측정하여 안정성을 조사하였다.The viscosity of the emulsion was measured using a Brookfield viscometer, and the stability was investigated by measuring the volume separated while filling and storing the emulsion in a 10 mL graduated cylinder.

Creaming Index (%) = HC / HE × 100Creaming Index (%) = H C / H E × 100

HC = 하단부 분리된 부분의 부피 H C = volume of the lower separated part

HE = 유화액의 총 부피H E = total volume of emulsion

<표 6><Table 6>

상기 표 6에 나타낸 것처럼, 세정수분말 및 세정수전분으로 제조한 OSA전분, 어닐링 OSA전분을 제조한 유화액의 점도를 측정한 결과 71.39~381.52 cp를 나타냈다. 이를 21일간 상온에서 저장하면서 유화액의 안정성을 측정한 결과를 아래 도 4와 같이 크리밍인덱스로 나타냈다. 낟알에서 분리한 전분의 경우 유화액 제조 2시간이 지났을 때 29%가 분리되었으나 세정수에서 분리한 전분은 2일 이후 서서히 분리되었고 21일이 지난 후 13%정도 분리되었다. 세정수 정제전분으로 OSA를 제조하여 유화액을 제조한 경우 21일까지 전혀 분리되지 않았다. 어닐링처리를 한 경우에도 21일까지 약 9%정도 분리되었으나 어닐링 처리와 OSA처리를 병행한 경우 유화액이 분리되지 않았다. 따라서 세정수에서 분리한 전분은 백미에서 분리한 전분이 비하여 유화안정성이 증가되며 OSA전분과 어닐링처리를 병행한 OSA전분 제조시 유화안정성이 크게 증가되었음을 알 수 있다.As shown in Table 6 above, the viscosity of the emulsion manufactured from the washed water powder and the washed water starch, and the annealed OSA starch was measured to be 71.39 to 381.52 cP. The stability of the emulsion was measured while storing it at room temperature for 21 days, and the result was expressed as a creaming index, as shown in Figure 4 below. In the case of the starch separated from the kernels, 29% was separated 2 hours after the emulsion was manufactured, but the starch separated from the washed water was gradually separated after 2 days and about 13% was separated after 21 days. When the emulsion was manufactured by manufacturing OSA with the washed water refined starch, it was not separated at all until 21 days. In the case of the annealing treatment, about 9% was separated until 21 days, but the emulsion was not separated when the annealing treatment and OSA treatment were performed together. Therefore, it can be seen that the starch separated from the washing water has increased emulsification stability compared to the starch separated from white rice, and that the emulsification stability is greatly increased when the OSA starch is manufactured by simultaneously performing annealing treatment with the OSA starch.

*찐만두용 만두피의 제조*Manufacturing of dumpling skin for steamed dumplings

찐만두용 만두피는 타피오카전분 68%, 감자전분 32%, 감미유와 소금을 혼합하여 95℃의 물을 첨가하여 반죽하였다. 이 중 타피오카 전분중 일부를 알파미분과 세정수전분, 변성전분으로 대체한 분말을 제조하여 기존만두피와 비교하였다. Dumpling skin for steamed dumplings was made by mixing 68% tapioca starch, 32% potato starch, sweetener, and salt, adding 95℃ water, and kneading the dough. Among these, a powder was manufactured by replacing some of the tapioca starch with alpha-micron powder, washed starch, and modified starch, and compared with the existing dumpling skin.

<표 7><Table 7>

상기 표 7에 나타낸 것처럼, 세정수 분말 및 OSA전분을 함유한 찐만두용 만두피의 냉해동안정성 측정결과, 기존 만두피분말의 타피오카 전분 중 4.6%를 세정수 전분 및 어닐링처리와 OSA 치환을 병행한 전분으로 대체하여 만두피분말을 제조하였고 냉해동 사이클을 1~5회 반복하여 냉해동 안정성을 측정하였다. 아래 도 5와 같이 냉해동 사이클 2회까지는 시료간에 큰 차이가 없었으나 3회차부터 이수율에 차이가 커졌다. 냉해동을 5회 반복한 결과 세정수전분을 대체한 경우 이수율이 기존 만두피 대비35.4~50.1% 감소하였고, 어닐링처리와 OSA를 병행한 경우 14.4~25.2%까지 감소하였다. 세정수에서 분리한 전분 자체도 냉해동 안정성이 개선에 효과가 있으나 어닐링 처리와 OSA처리를 병행하여 전분을 제조하여 만두피에 첨가할 경우 냉해동 안정성이 크게 개선될 수 있음을 알 수 있다.As shown in Table 7 above, the results of measuring the cold-thaw stability of dumpling skins for steamed dumplings containing washed water starch and OSA starch showed that 4.6% of the tapioca starch in the existing dumpling skin powder was replaced with washed water starch and starch that had undergone both annealing and OSA substitution to manufacture dumpling skin powder, and the cold-thaw stability was measured by repeating the cold-thaw cycle 1 to 5 times. As shown in Fig. 5 below, there was no significant difference between the samples up to the second cold-thaw cycle, but the difference in moisture content increased from the third cycle. As a result of repeating the cold-thaw cycle 5 times, when washed water starch was replaced, the moisture content decreased by 35.4 to 50.1% compared to the existing dumpling skin, and when annealing and OSA were combined, it decreased by 14.4 to 25.2%. Although starch itself separated from the washing water is effective in improving freeze-thaw stability, it was found that freeze-thaw stability can be significantly improved when starch is manufactured by simultaneously performing annealing treatment and OSA treatment and then added to the dumpling skin.

*세정수 분말 및 OSA전분을 함유한 찐만두용 만두피의 냉해동안정성 측정*Measurement of cold-thaw stability of dumpling skins for steamed dumplings containing cleansing water powder and OSA starch

세정수 분말 및 전분, OSA전분, 이로 제조한 만두피 분말로 6% 농도의 현탁액을 만들고 교반 가열하면서 호화액을 제조하여 마이크로 튜브에 1 g씩 넣어 상온에 냉각 후 4℃에서 24시간 저장하였다. -20℃ 냉동고에 20시간 동결하였으며 상온에서 4시간동안 해동한 후 원심분리기에서 3,000 rpm 속도로 10분간 원심분리하였다. 분리된 물을 버리고 남은 겔의 무게를 측정하여 이수율을 계산하였다. 냉동-해동 사이클은 1, 2, 3, 4, 5회까지 반복하였으며 그 때 분리된 물의 양을 측정하여 이수율을 비교하였다.A 6% concentration suspension was made with washing powder, starch, OSA starch, and dumpling skin powder made from these, and a gelatin solution was made by stirring and heating, placing 1 g each in a microtube, cooling to room temperature, and storing at 4°C for 24 hours. It was frozen in a -20°C freezer for 20 hours, thawed at room temperature for 4 hours, and centrifuged in a centrifuge at 3,000 rpm for 10 minutes. The separated water was discarded, and the weight of the remaining gel was measured to calculate the water content. The freeze-thaw cycle was repeated 1, 2, 3, 4, and 5 times, and the amount of water separated at that time was measured to compare the water content.

-세정수 분말 및 OSA전분을 함유한 찐만두용 만두피의 물성측정- Measuring the physical properties of dumpling skins for steamed dumplings containing cleansing water powder and OSA starch

세정수 분말 및 전분, 이로 제조한 OSA전분을 함유하는 찐만두용 만두피 분말을 혼합하여 95℃의 뜨거운 물을 부어 반죽한 후 증기가 오른 찜기에 넣어 30분간 가열하여 만두피를 제조하였고 1.0×1.0×1.0 cm로 성형하여 TA로 텍스쳐를 측정하였다.The dumpling skin powder for steamed dumplings containing washing water powder, starch, and OSA starch manufactured from the mixture was mixed, 95℃ hot water was poured in, kneaded, and placed in a steamer for 30 minutes to manufacture the dumpling skin, which was then shaped into 1.0×1.0×1.0 cm and the texture was measured using TA.

<표 8><Table 8>

상기 표 8에 나타낸 것처럼, 세정수 시료를 첨가하여 찐만두용 만두피를 제조한 후 물성을 측정한 결과. 세정수 정제전분과 침저분말, 어닐링OSA전분을 첨가한 만두피는 기존 만두피에 비해 경도와 부착성이 증가하고 응집성은 약간 감소하였으며 씹힘성이 증가되는 경향을 나타냈다.As shown in Table 8 above, the dumpling skins for steamed dumplings were manufactured by adding a washing water sample, and the results of measuring the physical properties were as follows. The dumpling skins with the addition of washing water, refined starch, precipitated powder, and annealed OSA starch showed increased hardness and adhesiveness, slightly decreased cohesiveness, and a tendency for increased chewiness compared to the existing dumpling skins.

찐만두용 만두피는 찐만두 유통과정과 같이 만두피를 -70℃에서 급속동결 후 냉동저장하였고 찐만두를 취식하는 방법대로 전자레인지로 재가열하여 물성을 측정하였다. 표 8과 같이 기존 만두피는 경도가 약 3배 증가하였고 첨가물에 따라 경도증가가 6배까지 증가하였으나 세정수 침전분말과 어닐링OSA전분을 첨가한 경우에는 경도가 유지되거나 감소하므로, 세정수 분말이나 어닐링OSA 전분은 냉동 찐만두의 식감을 개선시킬 수 있는 첨가제로 활용이 가능하다고 판단된다.The dumpling skin for steamed dumplings was quickly frozen at -70℃ and then stored in the freezer, similar to the distribution process for steamed dumplings, and its physical properties were measured by reheating it in a microwave oven in the same way as eating steamed dumplings. As shown in Table 8, the hardness of the existing dumpling skin increased by about 3 times, and depending on the additive, the increase in hardness increased up to 6 times, but when the washed water precipitated powder and annealed OSA starch were added, the hardness was maintained or decreased. Therefore, it is judged that the washed water powder and annealed OSA starch can be utilized as additives that can improve the texture of frozen steamed dumplings.

따라서, 본 발명에 따른 쌀세정수를 이용한 전분의 제조방법은 유화 안정성 및 냉해동 안정성이 월등하게 향상된 전분을 제공한다.Therefore, the method for manufacturing starch using rice washing water according to the present invention provides starch with significantly improved emulsification stability and freeze-thaw stability.

S101 ; 전분회수단계
S103 ; 증류수혼합단계
S104 ; 어닐링단계
S105 ; 호박산혼합단계
S107 ; 중화단계
S109 ; 원심분리단계
S111 ; 세척건조단계
S101; Starch recovery stage
S103; Distilled water mixing stage
S104; Annealing step
S105; Succinic acid mixing stage
S107 ; Neutralization stage
S109; Centrifugation step
S111; Washing and drying stage

Claims (7)

쌀세정수에서 전분을 회수하는 전분회수단계;
상기 전분회수단계를 통해 회수된 전분에 증류수를 혼합하는 증류수혼합단계;
상기 증류수혼합단계를 통해 제조된 혼합물에 무수옥테닐 호박산과 수산화나트륨을 혼합하는 호박산혼합단계;
상기 호박산혼합단계를 통해 제조된 혼합물을 중화하는 중화단계;
상기 중화단계를 통해 중화된 혼합물을 원심분리하는 원심분리단계; 및
상기 원심분리단계를 통해 분리된 전분을 세척한 후에 열풍건조하는 세척건조단계;로 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
Starch recovery step for recovering starch from rice washing water;
A distilled water mixing step of mixing distilled water into the starch recovered through the above starch recovery step;
A succinic acid mixing step of mixing anhydrous octenyl succinic acid and sodium hydroxide into the mixture prepared through the distilled water mixing step;
A neutralization step for neutralizing the mixture manufactured through the above succinic acid mixing step;
A centrifugation step for centrifuging the mixture neutralized through the above neutralization step; and
A method for manufacturing starch using rice washing water, characterized in that it comprises a washing and drying step of washing the starch separated through the centrifugal separation step and then drying it with hot air.
청구항 1에 있어서,
상기 증류수혼합단계와 상기 호박산혼합단계 사이에는 상기 증류수혼합단계를 통해 제조된 혼합물을 어닐링하는 어닐링단계가 더 진행되며,
상기 어닐링단계는 40 내지 50℃의 온도에서 20 내지 30시간 동안 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
In claim 1,
Between the distilled water mixing step and the succinic acid mixing step, an annealing step is further performed to anneal the mixture manufactured through the distilled water mixing step.
A method for manufacturing starch using rice washing water, characterized in that the above annealing step is performed at a temperature of 40 to 50°C for 20 to 30 hours.
청구항 1에 있어서,
상기 전분회수단계는 쌀세정수를 원심분리한 후에 침전물을 회수하고, 회수된 침전물을 질량농도가 0.2%인 수산화나트륨수용액으로 정제한 후에 1N 염산용액으로 중화하고 세척 및 건조하여 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
In claim 1,
The above starch recovery step is a method for manufacturing starch using rice washing water, characterized in that it comprises centrifuging rice washing water, recovering a precipitate, purifying the recovered precipitate with a sodium hydroxide aqueous solution having a mass concentration of 0.2%, neutralizing it with a 1 N hydrochloric acid solution, washing it, and drying it.
청구항 1에 있어서,
상기 증류수혼합단계는 상기 전분회수단계를 통해 제조된 전분 100 중량부에 증류수 180 내지 300 중량부를 혼합하여 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
In claim 1,
A method for manufacturing starch using rice washing water, characterized in that the distilled water mixing step is performed by mixing 180 to 300 parts by weight of distilled water with 100 parts by weight of starch manufactured through the starch recovery step.
청구항 1에 있어서,
상기 호박산혼합단계는 상기 증류수혼합단계를 통해 제조된 혼합물에 함유된 전분 100 중량부 대비 무수옥테닐 호박산 2 내지 4 중량부를 혼합하고, 수산화나트륨을 혼합하여 혼합물의 pH를 8 내지 9로 유지한 상태에서 5 내지 7시간 동안 반응하여 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
In claim 1,
A method for manufacturing starch using rice washing water, characterized in that the above succinic acid mixing step is performed by mixing 2 to 4 parts by weight of anhydrous octenyl succinic acid relative to 100 parts by weight of starch contained in the mixture manufactured through the above distilled water mixing step, mixing sodium hydroxide, and reacting the mixture for 5 to 7 hours while maintaining the pH of the mixture at 8 to 9.
청구항 1에 있어서,
상기 중화단계는 상기 호박산혼합단계를 통해 제조된 혼합물에 1N의 염산을 혼합하여 혼합물의 pH를 6.9 내지 7.1로 조절하여 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
In claim 1,
A method for manufacturing starch using rice washing water, characterized in that the neutralization step is performed by mixing 1N hydrochloric acid into the mixture manufactured through the succinic acid mixing step to adjust the pH of the mixture to 6.9 to 7.1.
청구항 1에 있어서,
상기 원심분리단계는 4500 내지 5500rpm의 속도로 8 내지 12분 동안 이루어지는 것을 특징으로 하는 쌀세정수를 이용한 전분의 제조방법.
In claim 1,
A method for manufacturing starch using rice washing water, characterized in that the centrifugation step is performed at a speed of 4,500 to 5,500 rpm for 8 to 12 minutes.
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